Multinuclear metallocene catalyst

ABSTRACT

The present invention relates to a multinuclear metallocene catalyst for olefin polymerization and a process for olefin polymerization using the same, in which the multinuclear metallocene catalyst for olefin polymerization comprises, as a main catalyst, a transition metal compound that contains at least two metal atoms in the groups III to X of the periodic table as central metals and a ligand having a cyclopentadienyl structure bridging between the two metal atoms, and, as a cocatalyst, an aluminoxane compound, an organoaluminum compound or a bulky compound reactive to the transition metal compound to impart a catalytic activity to the transition metal compound.

TECHNICAL FIELD

The present invention relates to a multinuclear metallocene catalyst forolefin polymerization containing at least two active sites and a highpolymerization activity, and a process for olefin polymerization usingthe same. More particularly, the present invention relates to amultinuclear metallocene catalyst for olefin polymerization and aprocess for olefin polymerization using the same, in which themultinuclear metallocene catalyst for olefin polymerization comprises asa main catalyst a transition metal compound containing at least twometal atoms in the groups III to X of the periodic table as centralmetals and a ligand having a cyclopentadienyl structure bridging betweenthe two metal atoms, and as a cocatalyst an aluminoxane compound, anorganoaluminum compound or a bulky compound reactive to the transitionmetal compound to impart a catalytic activity to the transition metalcompound.

BACKGROUND ART

Since the Ziegler-Natta catalyst was developed in the middle of the1950's, polyethylene, isotactic polypropylene and ethylene propylenediene copolymers (EPDM) of different properties have been produced. TheZiegler-Natta catalyst, of which the active sites are not uniform, isinapplicable to the preparation of polymers of narrow molecular weightdistribution MwD and compositional distribution.

An appearance of a metallocene catalyst in the middle of the 1980'senabled to produce polymers of various properties that are otherwiseimpossible to produce with the Ziegler-Natta catalyst, as well aspolymers of narrow molecular weight distribution and compositionaldistribution. In particular, the polymers of narrow molecular weightdistribution and compositional distribution that are polymerized usingthe metallocene catalyst have a high strength relative to the polymersof broad molecular distribution and compositional distributionpolymerized in the presence of the Ziegler-Natta catalyst, and reducethe stickiness in the manufacture of films or sheets. However, thosepolymers require an extremely high energy in processing because of itsnarrow molecular weight distribution.

Accordingly, many studies have been made in many countries of the worldon the multinuclear metallocene catalysts for the sake of overcoming thedrawbacks of the polymers of narrow molecular weight distribution.Examples of the related art can be described as follows.

First, U.S. Pat. No. 5,525,678 (Jun. 11, 1996) discloses a binuclearcatalyst system for olefin polymerization that comprises a metallocenecompound and a non-metallocene compound supported on a support, makingit possible to, produce a high molecular weight polymer and a lowmolecular weight polymer at once. But, the catalyst system requirescomplex processes in regard to independent supporting of the metallocenecompound and the non-metallocene compound and pretreatment of thesupport with different compounds for the supporting reaction.

U.S. Pat. No. 5,700,886 (Dec. 23, 1997) describes a polymerizationmethod using at least two metallocene compounds as catalysts in a singlereactor to control the molecular weight distribution of the polymer.This method is problematic in that a high expense for catalysts andstrict polymerization conditions are required in the polymerizationreaction to produce polymers of a desired molecular weight distributionbecause of using two or more metallocene compounds of a complicatedstructure.

Alternatively, U.S. Pat. No. 5,753,577 (May 19, 1998) discloses abinuclear metallocene compound containing two metal atoms in the groupIV of the periodic table as central metals, which have an oxidationnumber of +3 and are linked together by a direct chemical bond, themetallocene compound also having a chemical bond bridging betweenligands bonded to the central metals. The use of the catalyst forpolymerization, however, results in polymers having a low molecularweight.

U.S. Pat. No. 5,442,020 (Aug. 15, 1995) discloses an ethylene, propyleneor ethylene-alpha-olefin polymerization method using a binuclearmetallocene compound that is prepared by reacting a group IV metalcompound with an alkylene/silylene-bridged cyclopentadienyl group. But,the preparation of the catalyst requires a complex process in regard tointroduction of alkylene or silylene groups to the catalyst.

U.S. Pat. No. 5,627,117 (May 6, 1997) describes an ethylene, propyleneor ethylene-alpha-olefin polymerization method using a multinuclearmetallocene compound that is prepared by reacting a group IV to VIIImetal compound with a cyclopentadienyl group linked to alkylene orsilylene groups or divalent germanium (Ge) or tin (Sn). But, thecatalyst has a low activity for high-temperature polymerization relativeto the existing catalysts.

In addition, U.S. Pat. No. 6,010,974 (Jan. 4, 2000) discloses a styrenepolymerization method using a binuclear metallocene compound that isprepared by reacting a group IV metal compound with analkylene/silylene-bridged cyclopentadienyl group. The use of thiscatalyst is however limited to the preparation of styrene polymer orstyrene copolymer.

DISCLOSURE OF INVENTION

In an attempt to provide a catalyst for olefin polymerization that has ahigh polymerization activity and is used to produce polymers ofcontrollable molecular weight and the molecular weight distribution, theinventors of the present invention have found out that the problems withthe prior art can be solved by using a catalyst for olefinpolymerization that comprises as a main catalyst a transition metalcompound containing at least two metal atoms in the groups III to X ofthe periodic table as central metals and a ligand having acyclopentadienyl structure bridging between the two metal atoms, and asa cocatalyst an aluminoxane compound, an organoaluminum compound or abulky compound reactive to the transition metal compound to impart acatalytic activity to the transition metal compound, thereby completingthe present invention.

It is therefore an object of the present invention to provide a novelmultinuclear organometallic catalyst for olefin polymerization thatproduces polymers of controllable molecular weight and molecular weightdistribution in a homogenous or heterogeneous state and has a highpolymerization activity.

It is another object of the present invention to provide a process forolefin polymerization using the catalyst to prepare olefin polymershaving different molecular weights and various molecular weightdistributions.

To achieve the objects of the present invention, there is provided amultinuclear catalyst for olefin polymerization comprising: (A) atransition metal compound that has at least two metal atoms in thegroups III to X of the periodic table as central metals, and a ligand ofa cyclopentadienyl structure bridging between the two metal atoms; and(B) an aluminoxane compound, an organoaluminum compound, or a bulkycompound reactive to the transition metal compound to impart a catalyticactivity to the transition metal compound.

Hereinafter, the present invention will be described in more detail.

The catalyst for olefin polymerization according to the presentinvention comprises (A), as a main catalyst, a transition metal compoundthat contains at least two metal atoms in the groups III to X of theperiodic table as central metals and a ligand of a cyclopentadienylstructure bridging between the two metal atoms; and (B), as acocatalyst, an aluminoxane compound, an organoaluminum compound, or abulky compound reactive to the transition metal compound to impart acatalytic activity to the transition metal compound.

In the catalyst for olefin polymerization according to the presentinvention, the transition metal compound (A) as a main catalyst containsat least two metal atoms in the groups III to X of the periodic table ascentral metals and a ligand of a cyclopentadienyl structure bridgingbetween the two metal atoms, the transition metal compound beingrepresented by the formula 1:

wherein M¹ and M² are the same or different and each represents anelement in the groups III to X of the periodic table; Cp¹ and Cp² arethe same or different and each represents a ligand of an unsubstitutedor substituted cyclopentadienyl structure, the substitutedcyclopentadienyl structure having at least one substituent selected fromthe group consisting of a C₁-C₂₀ alkyl group, a C₃-C₂₀ cycloalkyl group,a C₁-C₂₀ alkylsilyl group, a C₁-C₂₀ haloalkyl group, a C₆-C₂₀ arylgroup, a C₆-C₂₀ arylalkyl group, a C₆-C₂₀ arylsilyl group, a C₆-C₂₀alkylaryl group, a C₁-C₂₀ alkoxy group, a C₁-C₂₀ alkylsiloxy group, aC₆-C₂₀ aryloxy group, a halogen atom and an amino group; and B¹represents a C₅-C₄₀ arylene group or an arylene group represented by theformula 2:Ary-(B^(1′))_(q)-Ary  [Formula 2]wherein Ary represents a C₆-C₂₀ arylene group directly bonded to Cp¹ andCp²; B^(1′) represents a C₁-C₂₀ alkylene group, a C₃-C₂₀ cycloalkylenegroup, a C₁-C₂₀ alkylsilylene group, a C₁-C₂₀ haloalkylene group, aC₆-C₂₀ arylalkylene group or a C₆-C₂₀ arylsilylene group; and q is aninteger from 0 to 5;

X and Y are the same or different and each represents Cp¹ or Cp², aC₁-C₂₀ alkyl group, a C₃-C₂₀ cycloalkyl group, a C₁-C₂₀ alkylsilylgroup, a C₁-C₂₀ haloalkyl group, a C₆-C₂₀ aryl group, a C₆-C₂₀ arylalkylgroup, a C₆-C₂₀ arylsilyl group, a C₆-C₂₀ alkylaryl group, a C₁-C₂₀alkoxy group, a C₁-C₂₀ alkylsiloxy group, a C₆-C₂₀ aryloxy group, ahalogen atom, an amino group or a tetrahydroborate group; a and b are aninteger from 1 to 5 determined by the oxidation number of the centralmetal; and p is an integer from 1 to 3.

Preferably, the transition metal compound represented by the formula 1is a transition metal compound represented by the formula 3, where p is1:

wherein M¹, M², Cp¹, Cp², B¹, X, Y, a and b are the same as defined theformula 1 and p is 1.

In the formula 1 of the transition metal compound used in the presentinvention, M¹ and M² are preferably an element in the group IV of theperiodic table, more preferably zirconium (Zr), titanium (Ti) or hafnium(Hf).

In the formula 1 of the transition metal compound used in the presentinvention, the ligand of the cyclopentadienyl structure of Cp¹ and Cp²includes, for example, a cyclopentadienyl group, an indenyl group or afluorenyl group. The substituent of the ligand of the cyclopentadienylstructure includes, for example, C₁-C₂₀ alkyl groups such as methyl,ethyl, propyl, butyl, pentyl and hexyl; C₃-C₂₀ cycloalkyl groups such ascyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; C₁-C₂₀ alkylsilylgroups such as methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl,diethylsilyl, trietlhylsilyl, propylsilyl, dipropylsilyl,tripropylsilyl, butylsilyl, dibutylsilyl and tributylsilyl; C₁-C₂₀haloalkyl groups such as trifluoromethyl; C₆-C₂₀ aryl groups such asphenyl, biphenyl, terphenyl, naphthyl, fluorenyl and benzyl; C₆-C₂₀arylalkyl groups such as phenylethyl and phenylpropyl; C₆-C₂₀ arylsilylgroups such as phenylsilyl, phenyldimethylsilyl, diphenylmethylsilyl andtriphenylsilyl; C₆-C₂₀ alkylaryl groups such as methylphenyl,dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl,triethylphenyl, propylphenyl, dipropylphenyl and tripropylphenyl; C₁-C₂₀alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentoxy andhexyloxy; C₁-C₂₀ alkylsiloxy groups such as methylsiloxy,dimethylsiloxy, trimethylsiloxy, ethylsiloxy, diethylsiloxy andtriethylsiloxy; C₆-C₂₀ aryloxy groups such as phenoxy, naphthoxy,methylphenoxy, dimethylphenoxy, trimethylphenoxy, ethylphenoxy,diethylphenoxy, triethylphenoxy, propylphenoxy, dipropylphenoxy andtripropylphenoxy; halogen atoms; or amino groups such as a dimethylamonogroup, a diethylamino group, a dipropylamino group, a dibutylaminogroup, a diphenylamino group and a dibenzylamino group. In the casewhere the cyclopentadienyl structure has at least two substituents, thesubstituents may be bonded together to form a ring compound.

In the formula 1 of the transition metal compound used in the presentinvention, Cp¹ and Cp² are preferably cyclopentadienyl,methylcyclopentadienyl, dimethylcyclopentadienyl,trimethylcyclopentadienyl, tetramethylcyclopentadienyl,ethylcyclopentadienyl, diethylcyclopentadienyl,triethylcyclopentadienyl, n-propylcyclopentadienyl,iso-propylcyclopentadienyl, n-butylcyclopentadienyl,iso-butylcyclopentadienyl, tert-butylcyclopentadienyl, indenyl,methylindenyl, dimethylindenyl, trimethylindenyl, ethylindenyl,diethylindenyl, or thiethylindenyl.

In the formula I-1 of the transition metal compound used in the presentinvention, B¹ is a divalent hydrocarbyl radical bridging between Cp¹ andCp². Examples of the arylene group as B¹ include phenylene, biphenylene,terphenylene, naphthylene, binaphthylene, fluorenylene, anthracylene,pyridylene, bipyridylene, terpyridylene, quinolylene, pyridazylene,pyrimidylene, pyrazylene, or quinoxalylene. Examples of B^(1′) includemethylene, dimethylmethylene, diethylmethylene, diphenylmethylene,ethylene, methylethylene, dimethylethylene, trimethylethylene,tetramethylethylene, tetraethylethylene, tetraphenylethylene, propylene,butylene, dimethylsilylene, diethylsilylene, diphenylsilylene,cyclohexylene, or tetrafluoroethylene.

In the formula 1 of the transition metal compound used in the presentinvention, B¹ is preferably phenylene, biphenylene,methylene-4,4′-biphenylene, 1,2-ethylene-4,4′-biphenylene,1,3-propylene-4,4′-biphenylene, 1,4-butylene-4,4′-biphenylene,terphenylene, anthracylene, or pyridylene.

In the formula 1 of the transition metal compound used in the presentinvention, X or Y preferably includes Cp¹ or Cp², C₆-C₂₀ aryloxy groups,or halogen atoms. More preferably, at least one of X and Y iscyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl,trimethylcyclopentadienyl, tetramethylcyclopentadienyl,pentamethylcyclopentadienyl, ethylcyclopentadienyl,diethylcyclopentadienyl, triethylcyclopentadienyl,n-propylcyclopentadienyl, iso-propylcyclopentadienyl,n-butylcyclopentadienyl, iso-butylcyclopentadienyl,tert-butylcyclopentadienyl, indenyl, methylindenyl, dimethylindenyl,trimethylindenyl, ethylindenyl, diethylindenyl, triethylindenyl,phenoxy, naphthoxy, methylphenoxy, dimethylphenoxy, trimethylphenoxy,ethylphenoxy, diethylphenoxy, triethylphenoxy, propylphenoxy,dipropylphenoxy, tripropylphenoxy, fluorine, chlorine, bromine, oriodine. The number of halogen atoms bonded to the central metal dependson the oxidation state of the central metal.

When p is 1 in the formula 1, the transition metal compound is aB¹-bridged binuclear transition metal compound as represented by theformula I-2; and when p is 2, the transition metal compound is aternuclear transition metal compound in which one more B¹ is linked toCp².

The preparation of the transition metal compound (A) represented by theformula 1 may include, if not specifically limited to, reacting all thecompounds of the following formulas 4, 5 and 6 at once, or reacting thecompound of the formula 4 with that of the formula 5 and then adding thecompound of the formula 6 to the resulting reactant, in which thecompound of the formula 5 may be the same as that of the formula 6:

wherein Cp¹, Cp², B¹ and p are as defined above in the formula 1; M³ isan alkali metal such as lithium (Li), sodium (Na) and potassium (K),aluminum (Al), or thallium (Tl); and r is an integer from 1 to 4;H-MX,  [Formula 5]wherein H is a halogen atom; and M¹, X and a are as defined above in theformula 1; andH-M²Y_(b)  [Formula 6]wherein H is a halogen atom; and M², Y and b are as defined above in theformula 1.

Alternatively, the transition metal compound (A) represented by theformula 3 may be prepared by reacting the compounds of the followingformulas 7 and 8:

wherein Cp¹, M¹, X and a are as defined above in the formula 3; and B¹¹is a substituent capable of forming B¹ in the reaction; and

wherein Cp², M², Y and b are as defined above in the formula 3; and B¹²is a substituent capable of forming B¹ in the reaction.

In the polymerization catalyst of the present invention, the aluminoxanecompound, the organoaluminum compound or bulky compound reactive to thetransition metal compound to impart the catalytic activity to thetransition metal compound used as a cocatalyst. The aluminoxane compound(B) is represented by the following formula 9 and has a linear, annularor network structure. Specific examples of the aluminoxane compoundinclude methylaluminoxane, ethylaluminoxane, butylaluminoxane,hexylaluminoxane, octylaluminoxane and decylaluminoxane.

wherein R¹ represents a C₁-C₁₀ alkyl group; and n is an integer from 1to 70.

In the polymerization catalyst of the present invention, theorganoaluminum compound (B) used as a cocatalyst is represented by thefollowing formula 10 and includes, for example, trialkylaluminum such astrimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum,trioctylaluminum and tridecylaluminum; dialkylaluminum alkoxide such asdimethylaluminum methoxide, diethylaluminum methoxide anddibutylaluminum methoxide; dialkylaluminum halide such asdimethylaluminum chloride, diethylaluminum chloride and dibutylaluminumchloride; alkylaluminum dialkoxide such as methylaluminum dimethoxide,ethylaluminum dimethoxide and butylaluminum dimethoxide; oralkylaluminum dihalide such as methylaluminum dichloride, ethylaluminumdichloride and butylaluminum dichloride.

wherein R², R³ and R⁴ are the same or different and each represents aC₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group or a halide group, at leastone of R², R³ and R⁴ including an alkyl group.

In the polymerization catalyst of the present invention, the bulkycompound (B) reactive to the transition metal compound to impart acatalytic activity to the transition metal compound is represented bythe following formula 11 and includes, for example, trimethylammoniumtetraphenylborate, triethylammonium tetraphenylborate, tripropylammoniumtetraphenylborate, tributylammonium tetraphenylborate, trimethylammoniumtetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tributylammoniumtetrakis(pentafluorophenyl)borate, anilium tetraphenylborate, aniliumtetrakis(pentafluorophenyl)borate, pyridinium tetraphenylborate,pyridinium tetrakis(pentafluorophenyl)borate, ferroceniumtetrakis(pentafluorophenyl)borate, silver tetraphenylborate, silvertetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)borane,tris(2,3,5,6-tetrafluorophenyl)borane ortris(3,4,5-triflurorophenyl)borane.[C][D]  [Formula 11]wherein C represents the proton-bonded cation of a Lewis base, or anoxidative metallic or non-metallic compound; and D is a compound of anelement in the groups V to XV of the periodic table and an organicsubstance.

The cocatalyst of the polymerization catalyst of the present invention,that is, the aluminoxane compound, the organoaluminum compound or thebulky compound reactive to the transition metal compound to impart acatalytic activity to the transition metal compound is not limited tothe above examples and may be used alone or in combination in the olefinpolymerization.

On the other hand, the polymerization catalyst of the present inventionmay be supported on a support such as an organic or inorganic compoundand used as a supported catalyst. To support the catalyst on thesupport, there may be used various methods, which may include supportingthe main catalyst (A) directly on a dehydrated support; pretreating thesupport with the cocatalyst (B) and then supporting the main catalyst(A) on the support; supporting the main catalyst (A) on the support andthen adding the cocatalyst (B); or reacting the main catalyst (A) withthe cocatalyst (B) and then with the support.

The support used for the polymerization catalyst of the presentinvention is not specifically limited and may be any inorganic compoundthat has fine pores on the surface and a large surface area. Examples ofthe inorganic compound used as the support may include silica, alumina,bauxite, zeolite, MgCl₂, CaCl₂, MgO, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO,ThO₂, or a mixture thereof, for example, SiO₂—MgO, SiO₂—Al₂O₃,SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—CrO₂O₃ or SiO₂—TiO₂—MgO. These compounds maycontain a small amount of carbonate, sulfate or nitrate. Examples of theorganic compound used as the support may include starch, cyclodextrine,or synthetic polymer.

Examples of the solvent used in supporting the polymerization catalystof the present invention may include aliphatic hydrocarbons such aspentane, hexane, heptane, octane, nonane, decane, undecane and docecane;aromatic hydrocarbons such as benzene, mono-chlorobenzene,dichlorobenzene, trichlorobenzene and toluene; or halogenated aliphatichydrocarbons such as dichloromethane, trichloromethane, dichloroethaneand trichloroethane. These solvents are used alone or in combinationduring the supporting method.

Though the amounts of the transition metal compound (A) and thealuminoxane compound (B), the organoaluminum compound (B) or the bulkycompound (B) reactive to the transition metal compound to impart acatalytic activity to the transition metal compound used in supportingthe polymerization catalyst of the present invention are notspecifically limited, the mole ratio of (B) to (A) is preferably 1 to10⁴:1, more preferably 1 to 5×10²:1.

The temperature for supporting the polymerization catalyst of thepresent invention is preferably 0 to 120° C., more preferably 20 to 100°C.

The polymerization reaction using the polymerization catalyst of thepresent invention may be performed in a slurry, liquid, gas or bulkstate. In the case of polymerization in the liquid or slurry state, thesolvent or olefin itself may be used as the medium and the olefin forthe polymerization reaction may be used alone or in combination of atleast two types. Examples of the solvent used in the polymerizationreaction may include butane, pentane, hexane, octane, decane, dodecane,cyclopentane, methylcyclopentane, cyclohexane, benzene, toluene, xylene,dichloromethane, chloroethane, 1,2-dichloroethane and chlorobenzene.These solvents may be used in combination at a predetermined mixingratio.

Examples of the olefin used in the olefin polymerization of the presentinvention may include C₂-C₂₀ α-olefin such as ethylene, propylene,1-butene, 1-pentene and 1-hexene; C₄-C₂₀ diolefin such as 1,3-butadiene,1,4-pentadiene and 2-methyl-1,3-butadiene; C₃-C₂₀ cycloolefin ordiolefin such as cyclopentene, cyclohexene, cyclopentadiene,cyclohexadiene, norbonene and methyl-2-norbonene; or unsubstituted orsubstituted styrene, the substituted styrene having a substituent suchas an alkyl group, a C₁-C₁₀ alkoxy group, a halogen group, an aminegroup, a silyl group or a halogenated alkyl group. These olefins may beused alone or in combination in the polymerization reaction.

Though the amount of the transition metal compound (A) for olefinpolymerization using the polymerization catalyst of the presentinvention is not specifically limited, the concentration of the centralmetal in the polymerization reaction system is preferably 10⁻⁸ to 10¹mol/l, more preferably 10⁻⁷ to 10⁻² mol/l.

Though the amount of the aluminoxane compound (B), the organoaluminumcompound (B) or the bulky compound (B) reactive to the transition metalcompound to impart a catalytic activity to the transition metal compoundused for the olefin polymerization of the present invention is notspecifically limited, the mole ratio of (B) to (A) is preferably 1 to10⁶:1, more preferably 1 to 5×10⁴:1.

The temperature for the olefin polymerization of the present inventionis not specifically limited and may be −50 to 200° C., preferably 0 to150° C. The olefin polymerization may be performed in a batch,semi-continuous or continuous system under the polymerization pressureof 1.0 to 3,000 atmospheres, preferably 2 to 1,000 atmospheres.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows an X-ray molecular structure of the compound prepared inSynthesis Example 1 of the present invention;

FIG. 2 shows an X-ray molecular structure of the compound prepared inSynthesis Example 3 of the present invention; and

FIG. 3 shows an X-ray molecular structure of the compound prepared inSynthesis Example 4 of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in further detailby way of the following synthetic examples and polymerization examples,which are not intended to limit the scope of the present invention.

SYNTHESIS EXAMPLES Synthesis of Transition Metal Compound (A)

All the syntheses were performed in the inert (e.g., nitrogen or argon)atmosphere using the standard Schlenk method and the glove box method.

For purification, there were used sodium-potassium alloy fortetrahydrofuran (THF), toluene and n-hexane, sodium-benzophenone ketylfor diethylether, or calcium hydride (CaH₂) for methylene chloride(CH₂Cl₂). Deuterium-substituted chloroform (CDCl₃) used in the analysisof the organometallic compounds was dried on an activated molecularsieve 4A.

Some compounds commercially available were used without any furtherpurification, examples of which may include 4,4′-dibromobiphenyl,1,4-dibromobenzene, 4-bromobenzyl bromide,2,3,4,5-tetramethyl-2-cyclopentenone, 2,6-diisopropylphenol,n-butyllithium (2.5M solution in n-Hexane), phenylmagnesium chloride(2.0M solution in THF), para-toluenesulfonic acid monohydrate(p-TsOH.H₂O), trimethylsilyl chloride (Me₃SiCl; TMSCl),triisopropoxytitanium chloride (ClTi(OiPr)₃), cyclopentadienylzirconiumtrichloride (CpZrCl₃) and pentamethylcyclopentadienyltitaniumtrichloride (Cp.TiCl₃).

¹H NMR and ¹³C NMR were measured with a Bruker Avance 400 spectrometer,and the element analysis was performed with an EA 1110-FISION (CEInstruments). The X-ray molecular structure was analyzed with anEnrarf-Nonius CAD4TSB diffractometer and interpreted throughcomputations on a Silicon Graphics Indigo2XZ workstation.

Synthesis Example 1 4,4′-biphenylenebis(2,3,4,5-tetramethylcyclopentadienyl) di(cyclopentanedienylzirconiumdichloride) ([4,4′-(C₅Me₄)₂(C₆H₄)₂][CpZrCl₂]₂) Synthesis Example 1—14,4′-bis(2,3,4,5-tetramethylcyclopentadienyl) biphenylene(4,4′-(C₅Me₄H)₂(C₆H₄)₂)

9.36 g (30 mmol) of 4,4′-dibromobiphenyl was mixed with 40 ml ofdiethylether to obtain a slurry and 24 ml (2 equivalent weights) ofn-butyllithium was added to the slurry at −30° C. The temperature wasthen raised to 0° C. to turn the reaction solution clear and produce aprecipitate (4,4′-biphenyl dilithium salt). At this temperature, thereaction solution was stirred for more 30 minutes, warmed to the roomtemperature and further stirred until the precipitate does not form anymore. After malting the precipitate settle and discarding thesupernatant, 30 ml of tetrahydrofuran was added and the reactionsolution was cooled to −78° C. To the reaction solution was slowly addeda solution prepared by dissolving 8.29 g of2,3,4,5-tetramethyl-2-cyclopentenone in 20 ml of tetrahydrofuran. Thereaction solution was then warmed to the room temperature and stirredovernight, and 30 ml of a saturated ammonium chloride (NH₄Cl) solutionwas added to terminate the reaction.

The organic layer was separated from the aqueous layer. The product wasmore extracted from the aqueous layer with 50 ml of diethylether and thediethylether layer was combined with the previously separated organiclayer. The combined organic layer was removed of the surplus water onanhydrous magnesium sulfate (MgSO₄). The solid was filtered out and acolorless oily product was obtained after evaporation of the solvent.

The product thus obtained was not purified but dissolved in 30 ml ofmethylene chloride at the room temperature. 0.1 g of p-toluenesulfonatehydrate in the solid state was added to immediately obtain an ivorysolid product. After stirred for more 30 minutes, the solid product wassubjected to vacuum until a small amount of methylene chloride remainsas to wet the solid product. 30 ml of n-hexane was added in order tofurther precipitate the solid product and dissolve the non-reactedsubstances. The ivory yellow solid product thus obtained was isolatedwith a glass filter, washed with each 30 ml of ethanol, diethylether andn-pentane in order and dried under vacuum to produce 7.50 g (63% yield)of the title compound.

¹H NMR (400.13 MHz, CDCl₃): d 7.61 (d, 4H), 7.30 (d, 4H), 3.22 (q, 2H),2.08 (s, 6H), 1.94 (s, 6H), 1.87 (s, 6H), 0.99 (s, 6H). ¹³C{¹H} NMR(100.62 MHz, CDCl₃): d 142.3, 140.9, 137.8, 137.5, 135.8, 135.2, 128.7,126.5, 50.0, 14.9, 12.9, 12.0, 11.1.

The synthesis process is presented in the following scheme 1.

Synthesis Example 1-2 4,4′-biphenylenebis(2,3,4,5-tetramethylcyclopentadienyl) di(Cyclopentanedienylzirconiumdichloride) ([4,4′-(C₅Me₄)₂(C₆H₄)₂][CpZrCl₂]₂)

0.592 g of 4,4′-bis(2,3,4,5-tetramethylcyclopentadienyl) biphenyleneprepared in Synthesis Example 1—1 was dissolved in 20 ml oftetrahydrofuran. 1.2 ml (2 equivalent weights) of n-butyllithium wasthen added to the reaction solution. The temperature was raised to theroom temperature with stirring overnight to obtain a brown solid productin the green-purple solution. The reaction solution was cooled down to−78° C. and 0.788 g (2 equivalent weights, 3.0 mmol) ofcyclopentadienylzirconium trichloride (CpZrCl₃) slurry in 10 ml oftetrahydrofuran was added to the reaction solution. The reactionsolution was warmed to the room temperature and stirred for more onehour to obtain a yellow solution, which was refluxed overnight withstirring. The light orange solution thus obtained was dried under vacuumand 30 ml of methylene chloride was added to the solution to dissolvethe product.

The methylene chloride solution was filtered out through a celite layerto obtain a yellowish green solution and methylene chloride wasvaporized to obtain a solid product, which was washed with 10 ml ofn-hexane/diethylether (v/v=2/1) twice and dried under vacuum to produce1.02 g (80% yield) the light yellowish title compound.

¹H NMR (400.13 MHz, CDCl₃): 7.69 (d, 4H), 7.25 (d, 4H), 6.17 (s, 10H),2.27 (s, 12H), 2.07 (s, 12H). ¹³C{¹H} NMR (100.62 MHz, CDCl₃): 138.9,133.3, 130.3, 126.8, 126.6, 126.2, 123.7, 116.7, 14.0, 12.3.

Anal. Calcd for C₄₀H₄₂Cl₄Zr₂: C, 56.72; H, 5.00. Found: C, 56.96; H,5.89.

The synthesis process is presented in the following scheme 1, and theX-ray molecular structure of 4,4′-biphenylenebis(2,3,4,5-tetramethylcyclopentadienyl) di(cyclopentanedienylzirconiumdichloride) is shown in FIG. 1.

Synthesis Example 2 4,4′-biphenylenebis(2,3,4,5-tetramethylcyclopentadienyl) di(titanium trichloride)([4,4′-(C₅Me₄)₂(C₆H₄)₂][TiCl₃]₂)

In the same manner as described in Synthesis Example 1-2, 1.97 g (5.0mmol) of 4,4′-bis(2,3,4,5-tetramethylcyclopentadienyl) biphenylene wasreacted with 2 equivalent weights of n-butyllithium.4,4′-bis(2,3,4,5-tetramethylcyclopentadienyl) biphenylene dilithium saltthus obtained was changed to slurry in 20 ml of tetrahydrofuran andadded to 20 ml of a tetrahydrofuran solution containing 2 equivalentweights of triisopropoxytitanium chloride (ClTi(OiPr)₃). The reactionsolution was warmed to the room temperature and stirred for more 3hours. After vaporizing tetrahydrofuran off, 30 ml of methylene chloridewas added to dissolve the reaction product. The methylene chloridesolution was filtered out through a celite layer and the solid byproductwas removed to obtain a light greenish solution. An excess oftrimethylsilyl chloride ((CH₃)₃SiCl, 3 equivalents, 11 ml) was thenadded to the solution at 0° C. The solution was warmed to the roomtemperature and stirred to observe that a red precipitate is slowlyformed. After stirring the reaction solution overnight, methylenechloride was vaporized to slightly wet the solid product, which waswashed with 20 ml of n-hexane/diethylether (v/v=2/1) twice and driedunder vacuum to produce 1.20 g (34% yield) of the title compound inscarlet fine crystals.

¹H NMR (400.13 MHz, CDCl₃): 7.70 (d, 4H), 7.46 (d, 4H), 2.51 (s, 12H),2.44 (s, 12H).

The synthesis process is presented in the following scheme 2.

Synthesis Example 3 4,4′-biphenylenebis(2,3,4,5-tetramethylcyclopentadienyl)di(2,6-diisopropylphenoxytitanium dichloride)([4,4′-(C₅Me₄)₂(C₅Me₄)₂(C₆H₄)₂][Ti(O-2,6-iPr₂Ph)Cl₂]₂)

0.351 g (0.5 mmol) of 4,4′-biphenylenebis(2,3,4,5-tetramethylcyclopentadienyl) di(titanium trichloride)prepared in Synthesis Example 2 and 0.184 g (2 equivalent weights) of2,6-diisopropylphenol lithium salt were added to the same reactor. Afteradding 20 ml of tetrahydrofuran at −78° C., the reaction solution wasslowly warmed to the room temperature and stirred for more 6 hours.Following the vaporization of tetrahydrofuran, the reaction product wasextracted with methylene chloride and passed through a celite pad toremove byproducts. Methylene chloride was vaporized to 10 ml. 20 ml ofn-hexane was added to the condensed solution to cause phase separationand cooled down to −20° C. to obtain 0.271 g (55% yield) of the titlecompound in red crystals.

¹H NMR (400.13 MHz, CDCl₃): 7.66 7.58 (m, 8H), 7.01 6.98 (m, 6H), 3.03(sept, 4H), 2.33 (s, 12H), 2.28 (s, 12H), 1.04 (d, 24H). ¹³C{¹H} NMR(100.62 MHz, CDCl₃): 159.9, 139.9, 139.6, 136.2, 133.6, 132.3, 131.1,130.9, 126.8, 123.6, 123.2, 26.8, 23.8, 14.0, 13.3.

Anal. Calcd for C₅₄H₆₆Cl₄O₂Ti₂: C, 65.87; H, 6.76. Found: C, 66.14; H,7.27.

The synthesis process is presented in the following scheme 2, and theX-ray molecular structure of 4,4′-biphenylenebis(2,3,4,5-tetramethylcyclopentadienyl)di(2,6-diisopropylphenoxytitanium dichloride) is shown in FIG. 2.

Synthesis Example 41,2-bis[4-{(2,3,4,5-tetramethylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride}phenyl]ethane (1,2-[4-{(C₅Me₄)CpZrCl₂}C₆H₄]₂(CH₂CH₂))Synthesis Example 4-1 1,2-di(4-bromophenyl)ethane(1,2-(BrC₆H₄)₂(CH₂CH₂))

4.718 g (20.0 mmol) of 1,4-bromobenzene was dissolved in 30 ml ofdiethylether, and the solution was cooled down to 0° C. 8.4 ml (1.1equivalent, 21 mmol) of n-butyllithium was dropped into the solutionwith a syringe. The solution was stirred for 20 minutes at 0° C. andcooled down to −78° C. to form a white precipitate. After making theprecipitate settle and discarding the supernatant, the precipitate wasdissolved in 30 ml of tetrahydrofuran (THF) at −78° C. In a separateflask, 4.998 g (20.0 mmol) of 4-bromobenzyl bromide was dissolved in 20ml of THF and the resulting solution was dropped into the precipitatesolution with a cannular. The mixed solution was slowly warmed to theroom temperature and stirred for more than 6 hours to form a lightyellowish brown solution and terminate the reaction. After adding anappropriate amount of a saturated ammonium chloride aqueous solution,the organic layer was extracted with 50 ml (×3) of diethylether, driedon anhydrous magnesium sulfate and then filtered. The solution wasremoved of the solvent on a rotary evaporator and subjected toseparation to obtain 2.890 g (85% yield) of a white solid product.

¹H NMR (400.13 MHz, CDCl₃): 7.36(d,4H), 6.96 (d, 4H), 2.82 (s, 4H).

Synthesis Example 4-21,2-di[4-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]ethane(1,2-[4-(C₅Me₄H)C₆H₄]₂(CH₂CH₂))

3.400 g (10 mmol) of 1,2-di(4-bromophenyl) ethane prepared in SynthesisExample 4-1 was dissolved in 50 ml of diethylether, and the solution wascooled down to 0° C. 8.4 ml (2.1 equivalents, 21 mmol) of n-butyllithiumwas dropped into the solution with a syringe. The solution was stirredfor one hour at 0° C., slowly warmed to the room temperature and thenstirred for more 2 hours to form a white precipitate. After malting theprecipitate settle and discarding the supernatant, the precipitate wasdissolved in 30 ml of THF at −78° C. In a separate flask, 2.764 g (20.0mmol) of 2,3,4,5-tetramethyl-2-cyclopentenone was mixed with 20 ml ofTHF and the resulting solution was dropped into the precipitate solutionwith a cannular. The mixed solution was slowly warmed to the roomtemperature and stirred for more than 6 hours to form a light yellowishsolution. After adding an appropriate amount of a saturated ammoniumchloride aqueous solution, the organic layer was extracted with 50 ml(×3) of diethylether, dried on anhydrous magnesium sulfate and thenfiltered. The solution was removed of the solvent on a rotary evaporatorto obtain a yellow sticky oil. This oil was dissolved in 50 ml ofmethylene chloride and then stirred with a catalytic amount (0.1 g) ofp-toluene sulfonate hydrate at the room temperature for 2 hours to forma yellowish solid. With the solvent vaporized on the rotary evaporatoruntil the solid was wet, the solid was washed with 30 ml of hexane andfiltered out. The yellowish solid was washed with 30 ml (×3) ofanhydrous ethanol and 30 ml (×2) of pentane and dried under vacuum toobtain 2.825 g (67% yield) of a yellowish solid.

¹H NMR (400.13 MHz, CDCl₃): 7.18(m, 8H), 3.17(q, 2H), 2.93(m, 4H),2.02(s, 6H), 1.91(s, 6H), 1.85(s, 6H), 0.95(d, 6H). ¹³C{¹H} NMR (1.00.62MHz, CDCl₃): 142.7, 140.4, 139.0, 136.7, 135.0, 134.8, 128.4, 18.1,50.1, 37.6, 14.9, 12.7, 11.9, 11.1.

Synthesis Example 4-31,2-bis[4-{(2,3,4,5-tetramethylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride}phenyl]ethane (1,2-[4-{(C₅Me₄)CpZrCl₂}C₆H₄]₂(CH₂CH₂))

0.422 g (1.0 mmol) of1,2-di[4-(2,3,4,5-tetramethylcyclopentadienyl)phenyl]ethane prepared inSynthesis Example 4-2 was dissolved in 30 ml of THF, and the solutionwas cooled down to −78° C. 1.0 ml (2.5 equivalents, 2.5 mmol) ofn-butyllithium was dropped into the solution with a syringe. Thesolution was slowly warmed to the room temperature and stirred for 4hours to form a yellowish precipitate. In a separate flask, 0.525 g (2.0mmol) of cyclopentadienylzirconium trichloride was dissolved in 20 ml ofTHF and the resulting solution was slowly dropped into the precipitatesolution with a cannular at −78° C. The mixed solution was slowly warmedto the room temperature and stirred for more than 24 hours to form ayellowish clear solution. The solution was dried under vacuum toevaporate the solvent to obtain a solid, which was dissolved in tolueneand removed of the remaining LiCl by celite-based filtration. Theresulting solution was dried under vacuum and, after adding anappropriate amount of pentane, cooled down to obtain 0.642 g (73% yield)of a yellowish solid.

¹H NMR (400.13 MHz, CDCl₃): 7.20 (d, 4H), 7.05 (d, 4H), 6.13 (s, 10H),2.99 (s, 4H), 2.22 (s, 12H), 2.05 (s, 12H). ¹³C{¹H} NMR (100.62 MHz,CDCl₃): 140.6, 131.7, 129.7, 128.5, 126.5, 126.1, 124.2, 116.7, 37.3,13.9, 12.3.

Anal. Calcd for C₄₂H₄₆Cl₄Zr₂: C, 57.65; H, 5.30. Found: C, 57.96; H,5.81.

The synthesis process is presented in the following scheme 3, and theX-ray molecular structure of1,2-bis[4-{(2,3,4,5-tetramethylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride}phenyl]ethane is shown in FIG. 3.

Synthesis Example 51,2-bis[4-{(3,4-dimethylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride}phenyl]ethane (1,2-[4-{(C₅Me₂H₂)CpZrCl₂}C₆H₄]₂(CH₂CH₂))Synthesis Example 5-11,2-bis[4-(3,4-dimethylcyclopentadienyl)phenyl]ethane(1,2-[4-(C₅Me₂H₃)C₆H₄]₂(CH₂CH₂))

3.400 g (10 mmol) of 1,2-di(4-bromophenyl) ethane prepared in SynthesisExample 4-1 was dissolved in 50 ml of diethylether, and the solution wascooled down to 0° C. 8.4 ml (2.1 equivalents, 21 mmol) of n-butyllithiumwas dropped into the solution with a syringe. The solution was stirredfor one hour at 0° C., slowly warmed to the room temperature and thenstirred for more 2 hours to form a white precipitate. After making theprecipitate settle and discarding the supernatant, the precipitate wasdissolved in 30 ml of THF at −78° C. In a separate flask, 2.183 g (20.0mmol) of 3,4-dimethyl-2-cyclopentenone was mixed with 20 ml of THF andthe resulting solution was slowly dropped into the precipitate solutionwith a cannular. The mixed solution was slowly warmed to the roomtemperature and stirred for more than 6 hours to form a light yellowishsolution. After adding an appropriate amount of a saturated ammoniumchloride aqueous solution to terminate the reaction, the organic layerwas extracted with 50 ml (×3) of diethylether, dried on anhydrousmagnesium sulfate and then filtered. The solution was removed of thesolvent on a rotary evaporator to obtain a yellowish sticky oil. Thisoil was dissolved in 50 ml of methylene chloride and mixed Faith acatalytic amount (0.1 g) of p-toluene sulfonate hydrate. The resultingsolution was stirred for 2 hours at the room temperature to form a lightbrown solid. With the solvent vaporized on the rotary evaporator untilthe solid was wet, the solid was washed with 30 ml of hexane andfiltered out. The solid was washed with 30 ml (×3) of anhydrous ethanoland 30 ml (×2) of pentane and dried under vacuum to obtain 2.314 g (63%yield) of an ivory solid.

¹H NMR (400.13 MHz, CDCl₃): 7.35 (d, 4H), 7.09 (d, 4H), 6.60 (s, 2H),3.24 (s, 4H), 2.86 (s, 4H), 1.96 (s, 6H), 1.87 (s, 6H). ¹³C{¹H} NMR(100.62 MHz, CDCl₃): 142.4, 139.7, 135.5, 135.4, 134.2, 131.0, 128.6,124.5, 45.3, 37.6, 13.4, 12.6.

Synthesis Example 5-21,2-bis[4-{(3,4-dimethylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride}phenyl]ethane (1,2-[4-{(C₅Me₂H₂)CpZrCl₂}C₆H₄]₂(CH₂CH₂))

0.367 g (1.00 mmol) of1,2-bis[4-(3,4-dimethylcyclopentadienyl)phenyl]ethane prepared inSynthesis Example 5-1 was dissolved in 30 ml of THF, and the solutionwas cooled down to −78° C. 1.0 ml (2.5 equivalents, 2.5 mmol) ofn-butyllithium was dropped into the solution with a syringe. Thesolution was slowly warmed to the room temperature and stirred for more4 hours to form an ivory precipitate. In a separate flask, 0.525 g (2.0mmol) of cyclopentadienylzirconium trichloride was dissolved in 20 ml ofTHF and the resulting solution was slowly dropped into the precipitatesolution with a cannular at −78° C. The mixed solution was slowly warmedto the room temperature and stirred for more than 24 hours to form alight yellowish solution. After vaporizing the solvent under vacuum, thesolid thus obtained was dissolved in toluene and removed of theremaining LiCl by celite-based filtration. The resulting solution wasdried under vacuum and, after adding an appropriate amount of pentane,cooled down to obtain 0.572 g (70% yield) of a light yellowish solid.

¹H NMR (400.13 MHz, CDCl₃): 7.35 (d, 4H), 7.12 (d, 4H), 6.50 (s, 4H),6.11 (s, 10H), 2.97 (s, 4H), 2.14 (s, 12H). ¹³C{¹H} NMR (100.62 MHz,CDCl₃): 140.8, 131.4, 129.4, 128.2, 125.1, 124.5, 116.5, 114.0, 37.3,13.8.

Anal. Calcd for C₃₈H₃₈Cl₄Zr₂: C, 55.74; H. 4.68. Found: C, 56.98; H,5.18.

The synthesis process is presented in the following scheme 4.

Synthesis Example Supported Catalyst

20 ml of toluene was added to 1 g of silica (Grace Davison #2412)calcinated in the nitrogen atmosphere at 800° C. for 12 hours. 2.38 ml(11.16 mmol) of methyl aluminoxane (MMAO, Witco AL 5100/30T) was addedat the room temperature, and the resulting solution was stirred for 10minutes. After adding 0.09 g (0.11 mmol) of 4,4′-biphenylenebis(2,3,4,5-tetramethylcyclopentadienyl) di(cyclopentanedienylzirconiumdichloride) prepared in Synthesis Example 1, the solution was stirredfor one hour and, after stopping the reaction, toluene was vaporized atthe room temperature. The supported catalyst thus obtained was washedwith an excess of toluene and the remaining toluene was completelyvaporized at the room temperature to obtain a light yellowish green freeflowing supported catalyst in the solid state, which was then dried at50° C. for more 30 minutes.

Comparative Synthesis Example Supported Catalyst

The procedures were performed in the same manner as described inSynthesis Example of Supported Catalyst, excepting that 0.032 g ofbis(cyclopentadienylzirconium) dichloride (Cp₂ZrCl₂) was used instead of0.09 g of 4,4′-biphenylene bis(2,3,4,5-tetramethylcyclopentadienyl)di(cyclopentanedienylzirconium dichloride).

Polymerization Examples Polymerization Example Using Non-SupportedCatalyst

All the polymerization reactions were performed under a predeterminedethylene pressure after injecting a defined amount of hydrogen, 1-hexeneand catalyst in an airtight autoclave. The molecular weight and themolecular weight distribution of the polymers thus obtained weremeasured by the gel permeation chromatography (GPC, PL-GPC220), and themelting point was measured by the differential scanning calorimetry(DSC, TA Instruments).

Polymerization Example 1

After introducing nitrogen into a stainless autoclave having an innervolume of 2 liters and adding 600 ml of toluene, there were sequentiallyadded 2 mmol of methyl aluminoxane (MAO (Witco, TA 02258/10HP)) based onthe Al atom and 0.5 μmol of 4,4′-biphenylenebis(2,3,4,5-tetramethylcyclopentadienyl) di(cyclopentanedienylzirconiumdichloride) prepared in Synthesis Example 1. The solution was heated to60° C. and, after introducing an ethylene gas, the polymerizationreaction was performed for one hour at 70° C. with the total pressure of6 bar·g. 50 ml of 10% HCl/MeOH was added to terminate the polymerizationreaction and the polymer thus obtained was washed with an excess ofmethanol and dried under vacuum at 60° C. for 15 hours. Thepolymerization results are presented in Table 1.

Polymerization Example 2

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 1, excepting that 0.03 barof hydrogen was introduced for polymerization.

Polymerization Example 3

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 1, excepting that 0.1 barof hydrogen was introduced for polymerization.

Polymerization Example 4

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 1, excepting that 0.4 barof hydrogen was introduced for polymerization.

Polymerization Example 5

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 1, excepting that 1.2 barof hydrogen was introduced for polymerization.

Polymerization Example 6

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 1, excepting that 10 ml of1-hexene was added for polymerization.

Polymerization Example 7

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 1, excepting that 30 ml of1-hexene was added for polymerization.

Polymerization Example 8

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 1, excepting that 50 ml of1-hexene was added for polymerization.

Polymerization Example 9

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 1, excepting that 0.1 barof hydrogen and 30 ml of 1-hexene were introduced for polymerization.

Polymerization Example 10

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 1, excepting that 600 mlof n-hexane was used as a solvent instead of toluene.

Polymerization Example 11

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 10, excepting that thepolymerization temperature was 60° C.

Polymerization Example 12

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 10, excepting that thepolymerization temperature was 80° C.

Polymerization Example 13

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 10, excepting that thepolymerization temperature was 90° C.

Polymerization Example 14

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 1, excepting that4,4′-biphenylene bis(2,3,4,5-tetramethylcyclopentadienyl) di(titaniumtrichloride) prepared in Synthesis Example 2 was used instead of4,4′-biphenylene bis(2,3,4,5-tetramethylcyclopentadienyl)di(cyclopentanedienylzirconium dichloride).

Polymerization Example 15

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 1, excepting that4,4′-biphenylene bis(2,3,4,5-tetramethylcyclopentadienyl)di(2,6-diisopropylphenoxytitanium dichloride) prepared in SynthesisExample 3 was used instead of 4,4′-biphenylenebis(2,3,4,5-tetramethylcyclopentadienyl) di(cyclopentanedienylzirconiumdichloride).

Polymerization Example 16

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 1, excepting that1,2-bis[4-{(2,3,4,5-tetramethylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride}phenyl]ethane prepared in Synthesis Example 4 was usedinstead of 4,4′-biphenylene bis(2,3,4,5-tetramethylcyclopentadienyl)di(cyclopentanedienylzirconium dichloride).

Polymerization Example 17

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 16, excepting that 600 mlof n-hexane was used as a solvent instead of toluene.

Polymerization Example 18

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 17, excepting that 0.1 barof hydrogen was introduced for polymerization.

Polymerization Example 19

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 17, excepting that 0.4 barof hydrogen was introduced for polymerization.

Polymerization Example 20

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 17, excepting that 1.2 barof hydrogen was introduced for polymerization.

Polymerization Example 21

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 17, excepting that thepolymerization temperature was 60° C.

Polymerization Example 22

The procedures for ethylene polymerization were performed in the samemauler as described in Polymerization Example 17, excepting that thepolymerization temperature was 80° C.

Polymerization Example 23

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 17, excepting that thepolymerization temperature was 90° C.

Polymerization Example 24

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 1, excepting that1,2-bis[4-{(3,4-dimethylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride}phenyl] ethane prepared in Synthesis Example 5 was usedinstead of 4,4′-biphenylene bis(2,3,4,5-tetramethylcyclopentadienyl)di(cyclopentanedienylzirconium dichloride).

Comparative Polymerization Example 1

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example 1, excepting that 1.0 μmolof bis(cyclopentadienyl)zirconium dichloride (Cp₂ZrCl₂) was used insteadof 4,4′-biphenylene bis(2,3,4,5-tetramethylcyclopentadienyl)di(cyclopentanedienylzirconium dichloride).

Comparative Polymerization Example 2

The procedures for ethylene polymerization were performed in the samemanner as described in Comparative Polymerization Example 1, exceptingthat n-hexane was used instead of toluene.

Comparative Polymerization Example 3

The procedures for ethylene polymerization were performed in the samemanner as described in Comparative Polymerization Example 1, exceptingthat pentamethylcyclopentadienyltitanium trichloride (CpTiCl₃) was usedinstead of biscyclopentadienylzirconium dichloride.

Polymerization Example Using Supported Catalyst

After introducing nitrogen into a stainless autoclave having an innervolume of 2 liters and adding 600 ml of n-hexane, there weresequentially added 2 mmol of triethylaluminum and 0.05 g of thesupported catalyst prepared in Synthesis Example of Supported Catalyst.The solution was heated to 60° C. and, after introducing an ethylenegas, the polymerization reaction was performed for one hour at 70° C.with the total pressure of 6 bar·g. 50 ml of 10% HCl/MeOH was added toterminate the polymerization reaction and the polymer thus obtained waswashed with an excess of methanol and dried under vacuum at 60° C. for15 hours. The polymerization results are presented in Table 2.

Comparative Polymerization Example Using Supported Catalyst

The procedures for ethylene polymerization were performed in the samemanner as described in Polymerization Example Using Supported Catalyst,excepting that the supported catalyst prepared in Comparative SynthesisExample of Supported Catalyst was used. The polymerization results arepresented in Table 2.

TABLE 1 Results of polymerization using non-supported catalyst. Hydrogen1-Hexene Catalyst Solvent (bar) (ml) Activity^(e) C D E A^(a) 1Synthesis  T^(c) 0 0 47.2 828 2.68 138.5 Example 1 2 Synthesis T 0.03 073.6 101 3.76 136.9 Example 1 3 Synthesis T 0.1 0 51.0 55.5 5.46 136.6Example 1 4 Synthesis T 0.4 0 49.1 34.3 9.17 133.4 Example 1 5 SynthesisT 1.2 0 30.2 65.4 53.0 127.9 Example 1 6 Synthesis T 0 10 20.8 721 3.35131.8 Example 1 7 Synthesis T 0 30 64.1 661 2.29 125.7 Example 1 8Synthesis T 0 50 41.5 552 3.41 122.6 Example 1 9 Synthesis T 0.1 30 90.6237 2.91 126.8 Example 1 10 Synthesis  H^(d) 0 0 26.4 712 2.97 141.0Example 1 11 Synthesis H 0 0  24.5^(f) 916 2.52 135.3 Example 1 12Synthesis H 0 0  24.5^(g) 586 2.53 139.1 Example 1 13 Synthesis H 0 0  9.43^(h) 391 3.10 137.5 Example 1 14 Synthesis T 0 0 6.5 457 2.82136.1 Example 2 15 Synthesis T 0 0 7.8 528 3.01 136.7 Example 3 16Synthesis T 0 0 45.1 1,250 2.57 140.0 Example 4 17 Synthesis H 0 0 25.11,089 2.42 137.7 Example 4 18 Synthesis H 0.1 0 24.1 172 4.6 136.0Example 4 19 Synthesis H 0.4 0 20.8 138 7.5 136.0 Example 4 20 SynthesisH 1.2 0 20.8 80 11.0 133.6 Example 4 21 Synthesis H 0 0  24.3^(f) 1,3202.48 140.5 Example 4 22 Synthesis H 0 0  23.8^(g) 607 2.52 139.6 Example4 23 Synthesis H 0 0  11.3^(h) 412 2.61 137.8 Example 4 24 Synthesis T 00 46.2 1,137 2.8 140.5 Example 5 B^(b) 1 Cp₂ZrCl₂ T 0 0 38.7 241 2.12139.9 2 Cp₂ZrCl₂ H 0 0 16.0 384 3.76 139.3 3 CpTiCl₃ ^(i) T 0 0 3.5 1032.75 136.1 A: Example B: Comparative Example C: Molecular weight (Mw)(×10⁻³) D: Molecular weight distribution (Mw/Mn) E: Melting point ofpolymer (° C.) ^(a)Polymerization Condition: P (ethylene), 6 bar; Tp 70°C.; tp, 1 h; [catalyst] 0.5 μmol; [Al]/[Zr], 2000 ^(b)[catalyst], 1.0μmol; [Al]/[Zr], 2000 ^(c)T, 600 ml toluene ^(d)H, 600 ml n-hexane^(e)Activity, (10³ kg of Polymer)/(mol of Zr) · h ^(f)Tp, 60 ° C.^(g)Tp, 80 ° C. ^(h)Tp, 90 ° C. ^(i)Activity, (10³ kg of Polymer)/(molof Ti) · h

TABLE 2 Results of polymerization using supported catalyst. SupportedHydrogen 1-Hexene Catalyst Solvent (bar) (ml) Activity^(b) C D E A^(a)Synthesis H^(c) 0 0 1.8 652 3.85 138.5 Example B  Comparative H  0 0 0.892.3 3.52 136.9 Example A: Example B: Comparative Example C: Molecularweight (Mw) (×10⁻³) D: Molecular weight distribution (Mw/Mn) E: Meltingpoint of polymer (° C.) ^(a)Polymerization Condition: P (ethylene), 6bar; Tp 70° C.; tp, 1 h; [supported catalyst] 0.05 g; TEA 2 mmole^(b)Activity, (kg of Polymer)/(g of Cat.) · h ^(c)H, 600 ml n-hexane

INDUSTRIAL APPLICABILITY

As described above, the catalyst for olefin polymerization according tothe present invention comprises, as a main catalyst, a transition metalcompound that contains at least two metal atoms in the groups III to Xof the periodic table as central metals and a ligand having acyclopentadienyl structure bridging between the two metal atoms, and, asa cocatalyst, an aluminoxane compound, an organoaluminum compound or abulky compound reactive to the transition metal compound to impart acatalytic activity to the transition metal compound, thereby effectivelyproducing polyolefin having various molecular weights and variousmolecular weight distributions.

1. A multinuclear catalyst for olefin polymerization comprising: (A) atransition metal compound represented by the formula 1:

wherein M¹ and M² are the same or different and each represents anelement in the groups III to X of the periodic table; Cp¹ and Cp² arethe same or different and each represents a ligand having anunsubstituted or substituted cyclopentadienyl structure, the substitutedcyclopentadienyl structure having at least one substituent selected fromthe group consisting of a C₁-C₂₀ alkyl group, a C₃-C₂₀ cycloalkyl group,a C₁-C₂₀ alkylsilyl group, a C₁-C₂₀ haloalkyl group, a C₆-C₂₀ arylgroup, a C₇-C₂₀ arylalkyl group, a C₆-C₂₀ arylsilyl group, a C₇-C₂₀alkylaryl group, a C₁-C₂₀ alkoxy group, a C₁-C₂₀ alkylsiloxy group, aC₆-C₂₀ aryloxy group, a halogen atom and an amino group; and B¹represents a C₁₂-C₄₀ arylene group or an arylene group represented bythe formula 2:  Ary-(B^(1′))q-Ary  [Formula 2] wherein Ary represents aC₆-C₂₀ arylene group directly bonded to Cp¹ and Cp²; B^(1′) represents aC₁-C₂₀ alkylene group, a C₃-C₂₀ cycloalkylene group, a C₁-C₂₀alkylsilylene group, a C₁-C₂₀ haloalkylene group, a C₇-C₂₀ arylalkylenegroup or a C₆-C₂₀ arylsilylene group; and q is an integer from 0 to 5; Xand Y are the same or different and each represents Cp¹ or Cp², a C₁-C₂₀alkyl group, a C₃-C₂₀ cycloalkyl group, a C₁-C₂₀ alkylsilyl group, aC₁-C₂₀ haloalkyl group, a C₆-C₂₀ aryl group, a C₇-C₂₀ arylalkyl group, aC₆-C₂₀ arylsilyl group, a C₆-C₂₀ alkylaryl group, a C₁-C₂₀ alkoxy group,a C₁-C₂₀ alkylsiloxy group, a C₆-C₂₀ aryloxy group, a halogen atom, anamino group or a tetrahydroborate group; a and b are an integer from 1to 5 determined by the oxidation number of the central metal; and p isan integer from 1 to 3; and (B) an aluminoxane compound represented bythe formula 9, an organoaluminum compound represented by the formula 10,or bulky compound represented by the formula 11 that is reactive to thetransition metal compound to impart a catalytic activity to thetransition metal compound:

wherein R¹ represents a C₁-C₁₀ alkyl group; and n is an integer from 2to 70;

wherein R², R³ and R⁴ are the same or different and each represents aC₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group or a halide group, at leastone of R², R³ and R⁴ is an alkyl group; and[C][D]  [Formula 11] wherein C represents a proton-bonded cation of aLewis base, or an oxidative metallic or non-metallic compound; and D isa compound of an element in the groups V to XV of the Periodic Table ofthe Elements and an organic substance.
 2. The multinuclear catalyst forolefin polymerization as claimed in claim 1, wherein the transitionmetal compound (A) is represented by the formula 3:

wherein M¹, M², Cp¹, Cp², B¹, X, Y, a and b are the same as defined theformula
 1. 3. The multinuclear catalyst for olefin polymerization asclaimed in claim 1, wherein M¹ and M² are an element in the group IV ofthe periodic table.
 4. The multinuclear catalyst for olefinpolymerization as claimed in claim 1, wherein the substituent of thecyclopentadienyl structure of Cp¹ and Cp² is at least one selected fromthe group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylsilyl,dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl,propylsilyl, dipropylsilyl, tripropylsilyl, butylsilyl, dibutylsilyl,tributylsilyl, trifluoromethyl, phenyl, biphenyl, terphenyl, naphthyl,fluorenyl, benzyl, phenylethyl, phenylpropyl, phenylsilyl,phenyldimethylsilyl, diphenylmethylsilyl, triphenylsilyl, methylphenyl,dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl,triethylphenyl, propylphenyl, dipropylphenyl, tripropylphenyl, methoxy,ethoxy, propoxy, butoxy, pentoxy, hexyloxy, methylsiloxy,dimethylsiloxy, trimethylsiloxy, ethylsiloxy, diethylsiloxy,triethylsiloxy, phenoxy, naphthoxy, methylphenoxy, dimethylphenoxy,trimethylphenoxy, ethylphenoxy, diethylphenoxy, triethylphenoxy,propylphenoxy, dipropylphenoxy, tripropylphenoxy, fluorine, chlorine,bromine, iodine, dimethylamino, diethylamino, dipropylamino,dibutylamino, diphenylamino, and dibenzylamino.
 5. The multinuclearcatalyst for olefin polymerization as claimed in claim 1, wherein Cp¹and Cp² are cyclopentadienyl, methylcyclopentadienyl,dimethylcyclopentadienyl, trimethylcyclopentadienyl,tetramethylcyclopentadienyl, ethylcyclopentadienyl,diethylcyclopentadienyl, triethylcyclopentadienyl,n-propylcyclopentadienyl, iso-propylcyclopentadienyl,n-butylcyclopentadienyl, iso-butylcyclopentadienyl,tert-butylcyclopentadienyl, indenyl, methylindenyl, dimethylindenyl,trimethylindenyl, ethylindenyl, diethylindenyl, or triethylindenyl. 6.The multinuclear catalyst for olefin polymerization as claimed in claim1, wherein the arylene group of B¹ is with or without heteroatom, andselected from biphenylene, terphenylene, naphthylene, binaphthylene,fluorenylene, anthracylene, pyridylene, bipyridylene, terpyridylene,quinolylene, pyridazylene, pyrimidylene, pyrazylene, or quinoxalylene.7. The multinuclear catalyst for olefin polymerization as claimed inclaim 1, wherein at least one of X and Y is a cyclopentadienyl,methylcyclopentadienyl, dimethylcyclopentadienyl,trimethylcyclopentadienyl, tetramethylcyclopentadienyl,pentamethylcyclopentadienyl, ethylcyclopentadienyl,diethylcyclopentadienyl, triethylcyclopentadienyl,n-propylcyclopentadienyl, iso-propylcyclopentadienyl,n-butylcyclopentadienyl, iso-butylcyclopentaienyl,tert-butylcyclopentaienyl, indenyl, methylindenyl, dimethylindenyl,trimethylindenyl, ethylindenyl, diethylindenyl, triethylindenyl,phenoxy, naphthoxy, methylphenoxy, dimethylphenoxy, trimethylphenoxy,ethylphenoxy, diethylphenoxy, triethylphenoxy, propylphenoxy,dipropylphenoxy, tripropylphenoxy, fluorine, chlorine, bromine, iodine,dimethylamino, diethylamino, dipropylamino, dibutylamino, diphenylamino,and dibenzylamino.
 8. The multinuclear catalyst for olefinpolymerization as claimed in claim 1, wherein the aluminoxane compound(B) is methylaluminoxane, ethylaluminoxane, butylaluminoxane,isobutylaluminoxane, hexylaluminoxane, octylaluminoxane, ordecylaluminoxane.
 9. The multinuclear catalyst for olefin polymerizationas claimed in claim 1, wherein the organoaluminium compound (B) istrialkylaluminum selected from the group consisting oftrimethylaluminum, triethylaluminum, tributylaluminumtriisobutylaluminum, trihexylaluminum, trioctylaluminum andtridecylaluminum and mixtures thereof; dialkylaluminum alkoxide selectedfrom the group consisting of dimethylaluminum methoxide, diethylaluminummethoxide, dibutylaluminum methoxide and diisobutylaluminum methoxideand mixtures thereof; dialkylaluminum halide selected from the groupconsisting of dimethylaluminum chloride, diethylaluminum chloride,dibutylaluminum chloride and diisobutylaluminum chloride and mixturesthereof; alkylaluminum dialkoxide selected from the group consisting ofmethylaluminum dimethoxide, ethylaluminum dimethoxide, butylaluminumdimethoxide and isobutylaluminum dimethoxide and mixtures thereof; oralkylaluminum dihalide selected from the group consisting ofmethylaluminum dichloride, ethylaluminum dichloride, butyaluminumdichloride and isobutylaluminum dichloride and mixtures thereof.
 10. Themultinuclear catalyst for olefin polymerization as claimed in claim 1,wherein the bulky compound (B) reactive to the transistion metalcompound to impart a catalytic activity to the transition metal compoundis trimethylammonium tetraphenylborate, triethylammoniumtetraphenylborate, tripropylammonium tetraphenylborate, tributylammoniumtetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate,triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tributylammoniumtetrakis(pentafluorophenyl)borate, anilium tetraphenylborate, aniliumtetrakis(pentafluorophenyl)borate, pyridinium tetraphenyborate,pyridinium tetrakis(pentafluorophenyl)borate, ferroceniumtetrakis(pentafluorophenyl)borate, silver tetraphenylborate, silvertetrakis (pentafluorophenyl)borate, tris(pentafluorophenyl)borane,tris(2,3,5,6-tetrafluorophenyl)borane, ortris(3,4,5-trifluorophenyl)borane.
 11. A supported catalyst for olefinpolymerization comprising the multinuclear catalyst for olefinpolymerization according to claim 1 supported on an organic or inorganicsupport.
 12. A supported catalyst for olefin polymerization as claimedin claim 11, wherein the inorganic support is silica, alumina, bauxite,zeolite, MgCl₂, CaCl₂, MgO, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂, or amixture thereof.
 13. A method for olefin polymerization comprisingpolymerizing olefins using the catalyst according to claim
 1. 14. Amethod for olefin polymerization comprising polymerizing olefins usingthe supported catalyst according to claim
 11. 15. The multinuclearcatalyst for olefin polymerization as claimed in claim 2, wherein M¹ andM² are an element in the group IV of the periodic table.
 16. Themultinuclear catalyst for olefin polymerization as claimed in claim 2,wherein the substituent of the cyclopentadienyl structure of Cp¹ and Cp²is at least one selected from the group consisting of methyl, ethyl,propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl,diethylsilyl, triethylsilyl, propylsilyl, dipropylsilyl, tripropylsilyl,butylsilyl, dibutylsilyl, tributylsilyl, trifluoromethyl, phenyl,biphenyl, terphenyl, naphthyl, fluorenyl, benzyl, phenylethyl,phenylpropyl, phenylsilyl, phenyldimethysilyl, diphenylmethylsilyl,triphenylsilyl, methylphenyl, dimethylphenyl, trimethylphenyl,ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl,dipropylphenyl, tripropylphenyl, methoxy, ethoxy, propoxy, butoxy,pentoxy, hexyloxy, methylsiloxy, dimethylsiloxy, trimethylsiloxy,ethylsiloxy, diethylsiloxy, triethylsiloxy, phenoxy, naphthoxy,methylphenoxy, dimethylphenoxy, trimethylphenoxy, ethylphenoxy,diethylphenoxy, triethylphenoxy, propylphenoxy, dipropylphenoxy,tripropylphenoxy, fluorine, chlorine, bromine, iodine, dimethylamino,diethylamino, dipropylamino, dibutylamino, diphenylamino, anddibenzylamino.
 17. The multinuclear catalyst for olefin polymerizationas claimed in claim 2, wherein Cp¹ and Cp² are cyclophentadienyl,methylcyclopentadienyl, dimethylcyclopentadienyl,trimethylcyclopentadienyl, tetramethylcyclopentadienyl,ethylcyclopentadienyl, diethylcyclopentadienyl,triethylcyclopentadienyl, n-propylcyclopentadienyl,iso-propylcyclopentadienyl, n-butylcyclopentadienyl,iso-butylcyclopentadienyl, tert-butylcyclopentadienyl, indenyl,methylindenyl, dimethylindenyl, trimethylindenyl, ethylindenyl,diethylindenyl, or triethylindenyl.
 18. The multinuclear catalyst forolefin polymerization as claimed in claim 2, wherein the arylene groupof B¹ is with or without heteroatom, and selected from biphenylene,terphenylene, naphthylene, binaphthylene, fluorenylene, anthracylene,pyridylene, biphenylene, terpyridylene, quinolylene, pyridazylene,pyrimidylene, pyrazylene, or quinoxalylene.
 19. A multinuclear catalystfor olefin polymerization comprising: (A) a transition metal compoundrepresented by the formula 1:

wherein M¹ and M² are the same or different and each represents anelement in the groups III to X of the Periodic Table of the Elements;Cp¹ and Cp² are the same or different and each represents a ligandhaving an unsubstituted or substituted cyclopentadienyl structure, thesubstituted cyclopentadienyl structure having at least one substituentselected from the group consisting of a C₁-C₂₀ alkyl group, a C₃-C₂₀cycloalkyl group, a C₁-C₂₀ alkylsilyl group, a C₁-C₂₀ haloalkyl group, aC₆-C₂₀ aryl group, a C₇-C₂₀ arylalkyl group, a C₈-C₂₀ arylsilyl group, aC₇-C₂₀ alkylaryl group, a C₁-C₂₀ alkoxy group, a C₁-C₂₀ alkylsiloxygroup, a C₈-C₂₀ aryloxy group, a halogen atom and an amino group; and B¹represents a C₁₂-C₄₀ arylene group or an arylene group represented bythe formula 2:Ary-(B^(1′))q-Ary  [Formula 2] wherein Ary represents a C₆-C₂₀ arylenegroup directly bonded to Cp¹ and Cp², B^(1′) represents a C₁-C₂₀alkylene group, a C₃-C₂₀ cycloalkylene group, a C₁-C₂₀ alkylsilylenegroup, a C₁-C₂₀ haloalkylene group, a C₇-C₂₀ arylalkylene group or aC₆-C₂₀ arylsilylene group; and q is an integer from 0 to 5; X and Y arethe same or different and each represents Cp¹ or Cp², a C₁-C₂₀ alkylgroup, a C₃-C₂₀ cycloalkyl group, a C₁-C₂₀ alkylsilyl group, a C₁-C₂₀haloalkyl group, a C₆-C₂₀ aryl group, a C₇-C₂₀ arylalkyl group, a C₆-C₂₀arylsilyl group, a C₆-C₂₀ alkylaryl group, a C₁-C₂₀ alkoxy group, aC₁-C₂₀ alkylsiloxy group, a C₆-C₂₀ aryloxy group, a halogen atom, anamino group or a tetrahydroborate group; a and b are an integer from 1to 5 determined by the oxidation number of the central metal; and p isan integer from 1 to 3; and (B) an aluminoxane compound represented bythe formula 9, an organoaluminum compound represented by the formula 10,or bulky compound represented by the formula 11 that is reactive to thetransition metal compound to impart a catalytic activity to thetransition metal compound:

wherein R¹ represents a C₁-C₁₀ alkyl group; and n is an integer from 2to 70;

wherein R², R³, R⁴ are the same or different and each represents aC₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group or a halide group, at leastone of R², R³, R⁴ is an alkyl group; and[C][D]  [Formula 11] wherein C represents a protonated cation of a Lewisbase, or an oxidative metallic or non-metallic compound; and D is acompound of an element found in groups V to XV of Periodic Table of theElements and an organic substance, wherein B^(1′) is methylene,dimethylmethylene, diethylmethylene, diphenylmethylene, ethylene,methylethylene, dimethylethylene, trimethylethylene,tetramethylethylene, tetraethylethylene, tetraphenylethylene, propylene,butylene, dimethylsilylene, diethylesilylene, diphenylsilylene,cyclohexylene or tetrafluoroethylene.
 20. A supported multinuclearcatalyst for olefin polymerization comprising: (A) a transition metalcompound represented by the formula 1:

wherein M¹ and M² are the same or different and each represents anelement in the groups III to X of the Periodic Table of the Elements;Cp¹ and Cp² are the same or different and each represents a ligandhaving an unsubstituted or substituted cyclopentadienyl structure, thesubstituted cyclopentadienyl structure having at least one substituentselected from the group consisting of a C₁-C₂₀ alkyl group, a C₃-C₂₀cycloalkyl group, a C₁-C₂₀ alkylsilyl group, a C₁-C₂₀ haloalkyl group, aC₆-C₂₀ aryl group, a C₇-C₂₀ arylalkyl group, a C₆-C₂₀ arylsilyl group, aC₇-C₂₀ alkylaryl group, a C₁-C_(°)alkoxy group, a C₁-C₂₀ alkylsiloxygroup, a C₆-C₂₀ aryloxy group, a halogen atom and an amino group; and B¹represents a C₁₂-C₄₀ arylene group or an arylene group represented bythe formula 2:Ary-(B^(1′))q-Ary  [Formula 2] wherein Ary represents a C₆-C₂₀ arylenegroup directly bonded to Cp¹ and Cp²; B¹′ represents a C₁-C₂₀ alkylenegroup, a C₃-C₂₀ cycloalkylene group, a C₁-C₂₀ alkylsilylene group, aC₁-C₂₀ haloalkylene group, a C₇-C₂₀ arylalkylene group or a C₆-C₂₀arylsilylene group; and q is an integer from 0 to 5; X and Y are thesame or different and each represents Cp¹ or Cp², a C₁-C₂₀ alkyl group,a C₃-C₂₀ cycloalkyl group, a C₁-C₂₀ alkylsilyl group, a C₁-C₂₀ haloalkylgroup, a C₆-C₂₀ aryl group, a C₇-C₂₀ arylalkyl group, a C₆-C₂₀ arylsilylgroup, a C₆-C₂₀ alkylaryl group, a C₁-C₂₀ alkoxy group, a C₁-C₂₀alkylsiloxy group, a C₆-C₂₀ aryloxy group, a halogen atom, an aminogroup or a tetrahydroborate group; a and b are an integer from 1 to 5determined by the oxidation number of the central metal; and p is aninteger from 1 to 3; and (B) an aluminoxane compound represented by theformula 9, an organoaluminum compound represented by the formula 10, orbulky compound represented by the formula 11 that is reactive to thetransition metal compound to impart a catalytic activity to thetransition metal compound:

wherein R¹ represents a C₁-C₁₀ alkyl group; and n is an integer from 2to 70;

wherein R², R³, R⁴ are the same or different and each represents aC₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group or a halide group, at leastone of R², R³, R⁴ is an alkyl group;[C][D]  [Formula 11] wherein C represents a protonated cation of a Lewisbase, or an oxidative metallic or non-metallic compound; and D is acompound of an element found in groups V to XV of Periodic Table of theElements and an organic substance; and an organic or inorganic support,wherein the organic support is starch, cyclodextrine, or syntheticpolymer.